Large quantities of methane, the main component of natural gas, are available in many areas of the world, and natural gas is predicted to outlast oil reserves by a significant margin. However, most natural gas is situated in areas that are geographically remote from population and industrial centers. The costs of compression, transportation, and storage make its use economically unattractive.
To improve the economics of natural gas use, much research has focused on methane as a starting material for the production of higher hydrocarbons and hydrocarbon liquids. The conversion of methane to hydrocarbons is typically carried out in two steps. In the first step, methane is reformed with water to produce carbon monoxide and hydrogen (i.e., synthesis gas or syngas). In a second step, the syngas is converted to hydrocarbons, for example, using the Fischer-Tropsch process to provide fuels that boil in the middle distillate range, such as kerosene and diesel fuel, and hydrocarbon waxes. Present day industrial use of methane as a chemical feedstock typically proceeds by the initial conversion of methane to carbon monoxide and hydrogen by either steam reforming, which is the most widely used process, or by dry reforming. Steam reforming proceeds according to Equation 1.
Although steam reforming has been practiced for over five decades, efforts to improve the energy efficiency and reduce the capital investment required for this technology continue.
The partial oxidation of hydrocarbons, e.g., natural gas or methane is another process that has been employed to produce syngas. While currently limited as an industrial process, partial oxidation has recently attracted much attention due to significant inherent advantages, such as the fact that significant heat is released during the process, in contrast to the steam reforming processes, which are endothermic. Partial oxidation of methane proceeds exothermically according to the following reaction stoichiometry:

In the catalytic partial oxidation (CPOX) processes, natural gas is mixed with air, oxygen or oxygen-enriched air, and is introduced to a catalyst at elevated temperature and pressure. The partial oxidation of methane yields a syngas mixture with a H2:CO ratio of about 2:1, as shown in Equation 2. This ratio is more useful than the H2:CO ratio from steam reforming for the downstream conversion of the syngas to chemicals such as methanol and to fuels. Furthermore, oxidation reactions are typically much faster than reforming reactions. This makes possible the use of much smaller reactors for catalytic partial oxidation processes. The syngas in turn may be converted to hydrocarbon products, for example, fuels boiling in the middle distillate range, such as kerosene and diesel fuel, and hydrocarbon waxes by processes such as the Fischer-Tropsch synthesis.
The selectivities of catalytic partial oxidation to the desired products, carbon monoxide and hydrogen, are controlled by several factors, but one of the most important of these factors is the choice of catalyst composition. Difficulties have arisen in the prior art in making such a choice economical. Typically, catalyst compositions have included precious metals and/or rare earths. The large volumes of expensive catalysts needed by the existing catalytic partial oxidation processes have placed these processes generally outside the limits of economic justification.
A number of process regimes have been described in the literature for the production of syngas via catalyzed partial oxidation reactions. The noble metals, which typically serve as the best catalysts for the partial oxidation of methane, are scarce and expensive. The more widely used, less expensive, catalysts have the disadvantage of promoting coke formation on the catalyst during the reaction, which results in loss of catalytic activity. Moreover, in order to obtain acceptable levels of conversion of gaseous hydrocarbon feedstock to CO and H2 it is typically necessary to operate the reactor at a relatively low flow rate, or space velocity, using a large quantity of catalyst. For successful operation at commercial scale, however, the catalytic partial oxidation process must be able to achieve a high conversion of the methane feedstock at high gas hourly space velocities, and the selectivity of the process to the desired products of carbon monoxide and hydrogen must be high. Such high conversion and selectivity must be achieved without detrimental effects to the catalyst, such as the formation of carbonaceous deposits (“coke”) on the catalyst, which severely reduces catalyst performance.
As a result, substantial effort has been devoted in the art to the development of economical catalysts allowing commercial performance without coke formation. Not only is the choice of the catalyst's chemical composition important, the physical structure of the catalyst and catalyst support structures must possess mechanical strength, in order to function under operating conditions of high pressure and high flow rate of the reactant and product gasses.
Of the methods that employ catalysts for oxidative conversion of methane, to syngas, typically catalytic metals are dispersed throughout a porous support. The porous support provides longitudinal channels or passageways that permit high space velocities with a minimal pressure drop. In ideal conditions, the catalytic metals are dispersed throughout the porous channels and promote further conversion.
The use of supports with internal pores can lead to insufficient use of catalyst because (i) the reactants do not have enough time to reach catalytic metals in the pores and (ii) the reactants may become trapped in the pores and interact in undesired secondary reactions during the diffusion of CO and H2 from the pores. Mass transfer rates can indeed control the rate of conversion, especially in short contact reactors.
Accordingly, there is a continuing need for better, more economical processes and catalysts for the catalytic partial oxidation of hydrocarbons, particularly methane, or methane containing feeds, in which the catalyst retains a high level of activity and selectivity to carbon monoxide and hydrogen under conditions of high gas space velocity and elevated pressure.
U.S. Pat. No. 6,281,385 discloses a process for preparing acetic acid by gas-phase oxidation of saturated C4-hydrocarbons and their mixtures with unsaturated C4-hydrocarbons in a tube reactor using a coated catalyst comprising an inert nonporous support body and a catalytically active mixed oxide composition comprising (a) one or more oxides selected from the group consisting of titanium dioxide, zirconium dioxide, tin dioxide and aluminum oxide and (b) from 0.1% to 1.5% by weight, based on the weight of the component (a) and per m2/g of specific surface area of the component (a), of vanadium pentoxide applied to the outer surface of the support body, wherein a gas mixture comprising oxygen or oxygen-containing gas, one or more C4-hydrocarbons and water vapor and having a C4-hydrocarbon/air (oxygen) volume ratio of from 0.2/99.8 to 25/75 and a C4-hydrocarbon/water vapor volume ratio of from 1/1 to 1/60 is reacted over the coated catalyst at a temperature of from 100° C. to 400° C. and a gauge pressure of from 0.2 to 50 bar.
U.S. published application No. 2002/0035033 discloses a process for preparing a shell-type catalyst which comprises applying to a substantially nonporous inorganic support material having a BET surface area of <80 m2/g, a catalytically active outer shell of a suspension containing at least one water soluble noble metal compound and a substantially water insoluble coating compound, drying the suspension onto the support material, and activating the coated support material in a reducing gas stream.
Despite these teachings, there remains a need for a catalyst system that is effective for carrying out fast partial oxidation reactions such as CPOX and oxidative dehydrogenation (ODH).